Automotive additive

ABSTRACT

A COMPOSITION SUITABLE FOR USE AS AN ADDITIVE TO MOTOR OILS, AS A MOTOR OIL SUBSTITUTE, AND/OR AS A FUEL ADDITIVE COMPRISING A POLYALKYLENE GLYCOL, A HYDROXYL-CONTAINING AROMATIC ESTER, A LOWER ALKANOL, A NATURALLY DERIVED AROMATIC KETONE, 3-P-MENTHANOL, AND A DYESTUFF WHICH COMPOSITION IS SUPERIOR TO CONVENTIONAL OILS AND/OR FUELS WITH REGARD TO THE AMOUNT POLLUTANTS GENERATED THEREFROM AS A RESULT OF THE USE THEREOF IN AN INTERNAL COMBUSTION ENGINE.

United States Patent Oflice 3,752,766 Patented Aug. 14, 1973 3,752,766AUTOMOTIVE ADDITIVE Clyde L. Wilson, P.0. Box 126, Incline Village, Nev.89450 No Drawing. Filed Dec. 14, 1970, Ser. No. 98,194 Int. Cl. C1011!1/20, N24 US. Cl. 25257 6 Claims ABSTRACT OF THE DISCLOSURE Acomposition suitable for use as an additive to motor oils, as a motoroil substitute, and/or as a fuel additive comprising a polyalkyleneglycol, a hydroxyl-containing aromatic ester, a lower alkanol, anaturally derived aromatic ketone, 3-p-menthanol, and a dyestuff whichcomposition is superior to conventional oils and/ or fuels with regardto the amount pollutants generated therefrom as a result of the usethereof in an internal combustion engine.

BACKGROUND OF THE INVENTION (1) Field of the invention The subjectapplication is directed to a novel composition which is particularlydesigned for use in connection with the operation of internal combustionengines. In particular, the subject composition is useful either as asubstitute for a lubricating oil, as a lubricating oil additive, and/oras a fuel for use in connection with such engines.

(2) Description of the prior art Ecology in general, and the pollutionof our environment which effects such ecology has become a matter ofnational concern towards which the efforts of government on all levelsincluding the federal, state and local governments of our country aredirecting a great deal of attention. Each day a new commission isestablished to study the effects of the day to day use of numerousproducts which we have in the past taken for granted, inasmuch as theyhave served to make our lives easier. Particular attention has beendirected toward discussing the numerous sources of pollutants which aredaily infiltrating the air which we breath. As a result of such efforts,it has become very apparent that there are several contributing factorswhich are presently very seriously effecting the ecological balance as aresult of the addition of unnatural and/or synthetic materials to theair. Inasmuch as most of the above-indicated efforts have shown that thepollution of the air is of critical importance with regard to ourcontinued existence, numerous efforts have been made to define thosefactors which are contributing most of such pollution, and further tocorrect same.

As a result of such efforts, there have been several indications thatthe use of the internal combustion engine, in automobiles is the largestcontributing factor to air pollution in this country. As a result of theuse of automobiles, trucks and similar conveyances, materials such ascarbon monoxide, hydrogen sulfide, hydrocarbon residues and the like areconstantly added to the air either because of the inefiiciency of theengine means employed in connection therewith, or as a result of ourinability to provide suitable fuels therfor which would eliminate suchinefficient combustion. Moreover, in addition to the contaminantsderived from fuels utilized in connection with such engines, furthercontamination has resulted from the lubricants conventionally therewith.

Such engines must, of course, be lubricated, in light of the heat andfriction which occur during the use thereof. If one were to eliminatelubricants from the internal structures of such an engine one wouldcause the engine to fail just as quickly as if fuel were withdrawntherefrom. That is to say, that the subject invention is directed toboth major sources of pollution which result from the use ofautomobiles, trucks and other conveyances as a result of the powersource utilized in connection therewith.

In light of the serious concern presently generated with regard topollution, numerous attempts have been made in the past to provide bothfuel and/or lubricating substitutes which would eliminate this primarycause of pollution. Such efforts have, however, been unsuccessful eitheras a result of the high costs of such additives thus, inhibiting thecommercial success thereof and/or the failure of technology to develop asuitable combination of materials which serve similar and/or identicalfunctions with regard to the materials which they are designed toreplace. That is to say, the manufacture of synthetic fuels is by thevery nature of the fuel which they are to replace a very complex anddifficult task. Internal combustion engines are designed to operate as aresult of the combustion of a fuel such as gasoline which results in theforced movements of the various parts contained therein. In order to bea suitable substitute, particularly for use in connection with presentlyexisting engines, a synthetic material must substantially duplicate thecharacteristics and properties of presently employed hydrocarbonderivatives. Moreover, it is noted that a synthetic material mustsubstantially duplicate the properties and/or actions of Presentlyavailable hydrocarbon derivatives at a reasonable cost in order to becommercially successful. As a result of the foregoing considera tions,the manufacture of synthetic additives and/or replacements has become anincreasingly diificult task towards which many millions of dollars ofresearch money have been directed.

SUMMARY OF THE INVENTION As previously noted the subject invention isdirected to a material which overcomes the numerous difficultiespreviously associated with the preparation of synthetic fuels and/orlubricants and, therefore, it is an object of the instant invention toprovide a synthetic material,- which will substantially replace fuelsand/or lubricants presently used in connection with automotive engines.

Another object of the instant invention is to provide a compositionwhich is useful as an additive to presently existing automotive fuelsand lubricants.

Yet another object of the instant invention is to provide a compositionwhich is substantially free of hydrocarbons which upon combustionpollute the air which composition serves as a fuel and/or lubricant foran internal combustion engine.

A still further object of the instant invention is to provide acomposition comprising a polyalkylene glycol base which is suitable foruse either as a replacement for or as an additive to internal combustionengine fuel and/ or lubricant.

These and other objects of the instant invention will become moreevident from the following more detailed description thereof.

As previously noted, the subject invention is directed to a compositionwhich is particularly designed for use in connection with internalcombustion engines. It has unexpectedly been found that the subjectcomposition serves both lubricating and fuel functions while drasticallyreducing the deleterious pollutants which results from the operation ofsuch engines. Therefore, such composition represents a substantial stepforward in the fight against pollution which is of such grave concern toall of us at this time.

As previously noted, the subject composition comprises a polyalkyleneglycol, an hydroxyl-containing aromatic ester, a naturally derivedaromatic ketone, 3-p-menthanol, a lower alkanol, and suitable dyestuffs.The subject polyalkylene glycols are, in general, mixtures having arelatively high average molecular weight and further comprise moleculescontaining polyalkylene chains formed predominantly of oxyethylenegroups, OC H and the oxy 1,2-propylene group, -OC H CH Moreover, suchpolyalkylene glycols are generally considered to be mixtures of truemonohydroxy aliphatic alcohol to a mixture of alkylene oxides containingethylene oxide and 1,2- propylene oxide in an oxide ratio of from 75-25to 10-90 ethylene oxide-1,2-propylene oxide. Such oxide ratio is definedto mean that in the oxide mixture which may be used in forming suchmonohydroxy alcohol addition products, the amount of 1,2-propylene oxidein the mixture is from A to 9 times the amount of ethylene oxide presentby weight, the parts are proportion of the 1,2-propylene oxide beinggiven last.

DETAILED DESCRIPTION OF THE INVENTION The polyalkylene glycols areprepared by a reaction which takes place between the alcohols, theethylene oxide, and the 1,2-propylene oxide which would appear to be asimple addition wherein the alkylene oxide molecules undergo conversionto the corresponding oxyalkylene radicals.

From such properties as the average molecular weight, refractive index,density, viscosity with change in temperature, as well as upontheoretical conditions its appears that these products are complexmixtures of monohydroxypolyoxyalkylene aliphatic monoethers havingpolyoxyalkylene chains of different lengths and different internalconfigurations with the hydroxyl group appearing at one end of the chainand the aliphatic group of the starting alcohol at the other, andfurther containing in the single molecules both the oxyethylene groupand the oxy 1,2-propylene group.

By way of illustration, the molecular weights of the oxyethylene-oxy1,2-propylene chains of compounds having oxyalkylene groups to themolecule would be 234, 248, 262, and 276 respectively exclusive of thealcohol depending on whether 1, 2, 3, 4, oxy 1,2- propylene groups arepresent therein; and in a mixture of such compounds the averagemolecular weight attributable solely to the oxyalkylene chain would bebetween 234 and 276 with the oxide ratio corresponding thereto beingbetween 75.2- 24.8 and 15.9-84.1. Similarly, the molecular weights ofthe oxyethylene-oxy 1,2-propylene chains of the compounds having sixoxyethylene groups to the molecule with 2, 3, 4 and 5 oxy 1,2-propylenegroups present therein would be 292, 306, 320 and 334, respectively; andin mixtures of such compounds the average molecular weight attributablesolely to the oxyalkylene chain would be between 292 and 334 with anoxide ratio between 60.3-39.7 and 13.2-86.8 corresponding thereto.Compounds having a singular oxypropylene group are omitted since theiroxide ratio falls below the 75-25 limit. In compounds having a total of7 oxyethylene and oxy 1,2-propylene groups to the molecule, of which thenumber of oxy 1,2-propylene groups are 2, 3, 4, 5, and 6, the molecularweight of the polyoxyalkylene chain would be 336, 350, 364, 378 and 392respectively; and in mixtures of such compounds the average molecularweight attributable solely to polyoxyalkylene chain would be between 336and 392, with an oxide ratio of between 65.5-34.5 and 11.2-88.8corresponding thereto. Likewise, in compounds having 2, 3, 4, 5, 6 and 7oxy 1,2-propylene groups in an oxyethylene oxy 1,2-propylene chain of 8oxyalkylene groups the molecular weights of such chains would be 380,394, 408, 422, 436 and 450 respectively with the average molecularweight attributable to the polyoxyalkylene chain in a mixture of suchcompounds being between 380 and 450, and the oxide ratio correspondingthereto being between 69.5- 30.5 and 9.8-90.2. To each of the foregoingvalues for molecular weights and average molecular weights there is tobe added a value not less than 32, i.e., the molecular weight ofmethanol the lowest member of the aliphatic alcohol series.

A product containing an admixture of the monohydroxy aliphaticmonoethers of the foregoing polyoxyalkylene chains having proportionsbetween 75-25 and 10-90 would have as many as 19 constituents (exclusiveof isomers) which differ from one another in the molecular weightsattributable to polyoxyalkylene chains yet which have a spread of onlyfrom 5 to 8 oxyalkylene groups between the smallest and largestmolecules, and a spread of from 266 to 482 in the molecular weights ofthe methylmonoethers. The complexities of the mixture may be due notonly to the diiference in molecular weights of the chains but also tothe large number of isomers which may be formed by random (i.e.,interspersed) distribution of the oxyethylene and oxy 1,2-propylenegroups, with constant variations in internal configuration from moleculeto molecule which complexity increases with the molecular weight.Moreover, such products may be referred to as mixtures of monohydroxyheterized oxyethylene oxy 1,2-propylene aliphatic monoethers. The termheterized is defined to mean that the monoethers vary in internalconfiguration from molecule to molecule, such variation arising out ofthe randomness of the distribution of the oxyethylene and the oxy1,2-propylene groups therein such as results for instance, from theconcurrent reaction of ethylene oxide and 1,2-propylene oxide with analiphatic monohydroxy alcohol.

Using ethylene oxide-1,2-propylene oxide ratios of from 75-25 to 10-90by weight and starting alcohols having 1, 2, 3, 4 and more carbon atomsto the molecule, numerous products have been manufactured having anaverage molecular weight ranging from about 500 to upwards of 5,000.Such polyalkylene glycols are normally obtained as liquid products whichare characterized by having a relatively low change of viscosity withchange in temperatures; the actual viscosity of the product as well asthe other properties such as density, refractive index, and the likebeing dependent solely on the starting materials, the oxide ratio, andthe average molecular weight. For a given starting alcohol and oxideratio the viscosity, density, and refractive index increase withmolecular weight, and for alcohols having from up to 14 or more carbonatoms and for oxide ratios from 75-25 to 10-90, the viscosities at agiven temperature appear to lie in a relatively narrow band or zonewhich, at a temperature of 210 F., extends from 3 to 10 centistokes atan average molecular weights of about 500 to 800, up to 20 to 50centistokes at average molecular weights of about 1500 to 2000. Foroxide ratios of from 50-50 to 10-90, at a temperature of 20 F., theviscosities extend from to 500 centistokes at average molecular weightsof about 500 to 800, up to 1500 to 5000 centistokes at average molecularWeights of 1500 to 2000.

In general, products containing a preponderance of 1,2- propylene oxideare preferred for use in connection with this invention. With anincrease in the 1,2-propylene oxide content the water tolerance of theproduct decreases and those products having an oxide ratio of about25-75, for instance, are substantially immiscible with water, even atlow temperatures; with the possible exception of low' average molecularweight compounds. Moreover, due to the difiiculties incumbent inmaintaining absolutely dry conditions, the subject polyalkylene glycolsmay have present therein in small amounts lower molecular weightcompounds, on the order of about 500-600 or less, and moreover, thepresence of such glycols may indicate an apparent water miscibility ofthe product which is not truly characteristic of the monoethers of whichit is essentially composed. Those polyalkylene glycols made frommixtures having oxide ratios of from about 50-50 to 10-90 which as notedare the preferred compounds for use in connection with the instantinvention are also characterized by the very useful property ofremaining in the fluid state at extremely low temperatures, forinstance, at temperatures as low as 50 C., and below. The temperature atwhich solidification of such compounds takes place increases with theincrease in the ethylene oxide content above 50%. Therefore, as noted,those compounds having less than 50% ethylene oxide are much preferredfor use in connection with the instant invention.

The ethylene oxide-l,2-yropylene oxide mixtures utilized in connectionwith the compositions of the instant invention may be prepared bybringing an ethylene oxidel,2-propylene oxide mixture into intimatecontact with a monohydroxy alcohol starting material in a liquid phasethroughout which a suitable catalyst is uniformly dispersed. For bestresults, it is essential that the addition reaction be carried out underconditions which are closely controlled with respect to such factors asthe amount of catalyst employed and the uniformity of its dispersion,the amount of unreacted alkylene oxides present at any stage during thereaction, the temperature maintained throughout the course of thereaction, and the intimacy and uniformity of contact of the reactingoxides with the reactants to which they are to be added.

Catalytic materials preferred for use in the preparation of suchcompositions are sodium hydroxide or potassium hydroxide in an amount offrom about 0.2 to about 1% by Weight of the total amount of thereactants, including the ethylene oxide and 1,2-propylene oxideappearing in the reaction product. An amount of active catalyst withinthis range is not so large as to cause excessive decomposition of thealkylene oxide addition product of the main reaction, and furtherexcellent results have been obtained with an amount of sodium hydroxidewhich is about 0.75% by weight of the reactants. The term activecatalysts as utilized herein is meant to define the amount of catalystpresent which has an alkalinity of the order of the alkali metalhydroxides, excluding such compounds of substantially less alkalinity asthe carbonates and carboxyl acid salts which may be titratable as thehydroxide. In addition to alkali metal hydroxides one may also employthe corresponding alcoholates thereof. In general, the stronger thealkalinity of the catalyst, the less one need employ in the reactionprocess. All of the catalysts, need not be added at the start of thereaction, and portions thereof may be added at the start with theremainder of the catalysts being added from time to time throughout thecourse thereof so as to maintain a substantially constant catalystsconcentration.

Some of the reaction conditions, such as, for example, high reactiontemperature, would appear to favor the formation of glycols of lowmolecular weight, and any tendency toward glycol formation may becomemore pronounced the higher the reaction temperature. The oxyalkyleneglycols thus formed are in small amount of the preferred reactionconditions, however, and may be removed by a subsequent treatment, suchas, for example, distillation, extraction or both.

The reaction should be carried out at a temperature which issufiiciently high to favor reaction of the alkylene oxides. A rapidreaction rate reduces the time of exposure of the oxide to the catalystand the surfaces of the reaction vessel, therefore, decreasing thepossibility of isomerization, and the formation of side reactionproducts. With the preferred alkaline catalysts, dry sodium hydroxide orpotassium hydroxide or the corresponding alcoholates thereof, reactiontemperatures of from about 80 C. to about 160 C. have been used. At suchtemperatures productspossessing excellent properties for use in thesubject lubricating and/or fuel additive compositions which do notdeposit sludge, gumor lacquer-film forming materials, or corrode metalparts when used therein have resulted.

It is further noted that preferably one avoids an excessiveconcentration of underreacted alkylene oxides in the reaction zone,especially in the presence of the strongly alkaline catalysts such assodium hydroxide, potassium hydroxide, or the alkali metal alcoholates.It is preferred to supply the ethylene oxide and 1,2-propylene oxide tothe reaction zone at such a rate which enables one to maintain a controlconcentration of unreacted oxides which is substantially uniform orconstant to the end of the reaction. To this end, the reaction ispreferably performed in a closed system and said oxides are introducedat a rate which maintains a substantially uniform pressure therein. Saidpressure should be maintained at about 5 to 50 p.s.i., although underother conditions pressures as high as 200 p.s.i. may also be employed.It is also noted that a nonreactive gas, such as, for example, nitrogen,may be utilized to assist in maintaining such pressure. Furthermore, itis suggested that the liquids in the reaction vessel either be cycledand/or agitated vigorously so as to wash the walls thereof and assist inmaintaining the intimate contact and uniform concentration of thereactants. Because the presence of oxygen tends to favor the formationof side reaction products, the reaction vessel should be exhausted orthe air swept out therefrom, with gaseous nitrogen or the like prior tocharging the reactor.

It is also noted that a more stable composition results if themonohydroxy heterized oxyethylene 1,2-propylene aliphatic monoetherproducts utilized therein have a low ash content so as to diminishand/or void such formation and the deposition of carbon. The ashcontents of the addition product may be derived from the catalyst usedin making same, and also from any ash forming inorganic impuritiespresent in the reactants or acid substances present in the reactionmixture. In removal and/or absence of low molecular weight glycols andthe water associated therewith, greatly decreases the solubility of suchash forming impurities and, therefore, the subject heterized monoetherproducts are relatively free from such impurities.

For best control, it is desirable to carry out the oxide addition underrelatively moisture free conditions, and to avoid side reactions whichform water. Therefore, the dry reaction vessels and connections arepreferably swept out with dry oxygen free gas as noted above prior tointroducing the charge. The catalyst should also be dry or substantiallyso. The ethylene oxide and 1,2-propylene oxide should preferably bepurified to remove the moisture and impurities therefrom which moistureand impurities are capable of entering into side reactions which yieldwater. Moreover, compositions of superior stability, with an averagemolecular weight of about 1,000 to 3,500 or higher, and which have onlyrelatively small amounts of polyoxyalkylene glycols of a molecularweight of about 500-600 and lower, are produced when the moisturecontent of the oxides does not exceed about 0.1% by weight. For bestresults, a low ash content and good stability are required, and,therefore, a moisture content of less than 0.05% is desirable. It isrecognized, however, that there may be a minimum amount or trace ofmoisture which is essential, and below which it is undesirable to go.

Alkaline oxides of a desired degree of dryness may be obtained bydistilling same through an efiicient rectifying column or from solutionin a hygroscopic glycol or the like, for instance, ethylene glycol,diethylene glycol, propylene glycol or the higher members of the glycolseries. The oxide vapor may also be scrubbed by means of a hygroscopicliquid and the like.

When a strongly alkaline catalyst such as, for example, sodium hydroxideis employed, it is also preferred to neutralize said catalyst uponcompletion of the reaction, with an acid which will react with thecatalyst to form a salt having characteristics which favor its removalfrom the reaction product. To this end sulfuric acid and carbon dioxidehave been employed with said sulfuric acid being utilized in its diluteaqueous form. When neutralizing the catalyst, it is also desirable toform salts which are insoluble in the reaction product after strippingit of the low boiling constituents, and which may be removedmechanically as by filtering at a relatively high temperature.

Impurities other than inorganic salts which may be formed in thereaction products under some conditions may include, for instance, watersoluble materials which are not the monohydroxy aliphatic monoethersutilized herein. Because of the relatively high molecular weight of saidmonoethers, they cannot be readily distilled in ordinary vacuumequipment, and for the removal of the water soluble impurities it may bedesirable to carry out an extraction step, preferably prior to thestripping operation. Water, or an aqueous salt solution may be utilizedas the extractant. Such an extraction may be carried out advantageouslyat moderately elevated temperatures of from about 50 C. to 95 C., orhigher and under pressure if need be, because of the decreasedmiscibility of the product with water and aqueous salt solutions at suchtemperatures, especially with products of higher oxyethylene content. Incarrying out the extraction it has also been found that the effect ofsodium carbonate in favoring the formation of two phases is quite markedand that in many cases, two phases may be formed at normal roomtemperature by saturating an aqueous solution with sodium carbonate orpotassium carbonate. When two phases have developed by heating orsalting out, an appreciable amount of the monohydroxy addition productmay remain in the water or extract phase. Some of the water may alsoremain in the ralfinate stage. Upon adding a third component which is asolvent for the product but a non-solvent for the water, the productsolvent phase will contain less water, and less product will be presentin the extract phase. Solvents which are suitable as assistants inmaking such extractions are dichloro diethyl ether, dibutyl ether,butanol, hexanol, toluene, benzene, ethylene dichloride, and the like.By dissolving the product in such a solvent and washing the resultantsolution at a temperature of about 95 to 98 C. with successive smallportions of water, a substantially ash free raflinate may be obtainedwith but slight loss of product. Subsequent to removing the solvent fromthe raflinate or solvent product phase, by distillation or the like, theresidue may be stripped of low boiling constituents by heating sameunder a reduced pressure which may be as low as about 1 or 2 millimetersof mercury and at an elevated temperature which may reach 180 C. orhigher. The use of a solvent is especially suitable in extracting thoseproducts which do not readily form two phases on heating with aqueoussolutions to about 100 C. Materials appearing in the extract or aqueousphase may be recovered by removing the water, as by distillation, andfiltering the residue to remove the salt therefrom. When the extractionis properly carried out, the stability of the raffinate and its freedomfrom corrosive action allows for the preparation of a unique lubricatingand/or fuel substituted or additive.

It is also noted that one may prepare the monoethers utilized in thesubject composition with catalysts other than alkali metal hydroxides.Boro and trifluororide for instance may be utilized in making suchproducts having an average molecular weight of up to about 1,000.Products having an average molecular weight above this value are notreadily prepared with boro and trifiuoride and if so prepared, theproducts therefrom though useful have properties which diifer somewhatfrom those of the caustic catalyzed products which are preferred for usein the subject compositions. In low concentrations, boro and trifiuorideis also more active as a catalyst than sodium hydroxide, and an amountof the trifiuoride which is about 0.15 to 0.5% of the total weight ofthe reactants may be used with good results. A uniform concentration ofabout 0.15%, however, is preferred. With said boro and trifiuoridecatalysts, reaction temperatures of from about 50 to 130 C. have beenused with good results, but, preferably a temperature of about 70 to 90is employed. It is also noted that the corrosive action of the boro andtrifiuoride on metal equipment and also the possibility of sidereactions may be avoided by the addition of small amounts of calciumoxide to the reactants. Upon completion of the reaction, theneutralization of the catalysts by adding lime in th presence of waterresults in the formation of salts which may be removed by filteringand/or extraction. In the event the boro and trifiuoride catalyzedproduct is desired for use in the composition of the instant inventionit is highly desirable to remove the fluorine therefrom so as to providean ultimate composition having superior stability.

In particular, the polyalkylene glycols which are consideredparticularly useful in connection with the instant invention have anethylene oxide-1,2-propylene oxide ratio of from about 50-50 to about10-90. They may vary in certain basic characteristics properties and maybe generally designated by their visosity in Saybold Universal Seconds(SUS) at F. which ranges from about 50 to more than 300,000. The subjectcompounds show less change in viscosity with temperature than dopetroleum oils and further represent an advantage thereover in light ofthe fact that they can be specifically controlled and varied with adegree not possible with naturally occuring, refined hydrocarbonlubricants. The viscosities of the subject compounds may vary from aboutto about 155 (A.S.T.M. 11567). Moreover, the subject polyalkyleneglycols have low stable pour points and are extremely chemically stablecompounds which under conditions of high temperature and the like do nottend to break down. Furthermore, when said compounds od disintegratethey tend to form soluble fluids or volatile products as distinguishedfrom sludge or varnish which is conventionally associated with thedegradation of lubricants and/or fuels. In addition, it is noted thatthe subject compounds are free from carbon or coke and thus, aspreviously noted, they do not contribute to the pollution of ourenvironment and as a result of such freedom from carbon and coke thesubject polyalkylene glycols in the presence of air result in anextremenly clean burn-off.

It is further noted that said polyalkylene glycols have, in addition tothe above-noted advantages, further advantages including theirnon-corrosive nature to the internal parts of an internal combustionengine, their unreactive nature with rubber which comprises the majorityof gas surfaces and the like.

The particular polyalkylene glycol utilized in connection with theinstant invention may be determined based upon commercial, and ultimatepurpose requirements. That is to say, that anyone of numerouspolyalkylene glyuols within the above-noted classification may beemployed in connection herewith. Such materials should preferably,however, be water-insoluble and have a viscosity index of approximatelyfrom about to (A.S.T.M. D5 67). Moreover, such compounds should have aviscosity in Saybold Seconds at 210 F., of from about 50 to about 80,and from about 200 to about 500 at 100 F. Moreover, at 0 F., suchcompounds should have a viscosity in Saybold Seconds of from about15,000 to about 30,000. It is also preferred that the subjectpolyalkylene glycols have a pour point of from about 0 to about --50 F.and a density of from about 0.9 to about 1 at temperatures of from about60 F. to about 210 F. Still further such polyalkylene glycols shouldhave a coefficient of expansion of from about 0.00040 to about 0.00050per degree Fahrenheit and a water content of less than 0.25 percent.

It is preferred, however, to employ in a lubricant or lubricant-additivecomposition those polyalkylene glycols having a relatively low viscositywhile employing those polyalkylene glycols with a high viscosity inconnection with fuel substitutes and/or additives.

The second ingredient of the subject composition is a naturally derivedaromatic ketone which is preferably, derived from Cinnammomum camphora.Such a ketone has a molecular weight of approximately 152.2 and occursas a colorless white crystals, granules, or crystalline masses.Moreover, such a ketone has a specific gravity of approximately 0.99 andis slowly volatile at room temperature, has a solubility ofapproximately 1 to in hexane and a melting point of from about 174 to179. Representative of such a ketone is a compound having the formula:

CHI CHr-C-CH: ;=o

3-p-methanol is the third component of the subject composition, whichcompound has a molecular weight of approximately 156.27 and occurs ascolorless hexanol crystals. Moreover, the compound has a melting rangeof from about 41 to about 43 and is freely soluble in organic solvents.I

The fourth components of the subject invention comprises anhydroxyl-containing aromatic ester having the general formula:

wherein A represents an aromatic nucleus, X is a carboxyl substituent, Ris a substituent selected from the group consisting of hydrogen, hydroxyalkyl, hydroxyl and the like and a is a whole number of at least 1 and bis zero or a whole number. Preferably, however, the subjecthydroxy-containing aromatic ester has a formula:

COOCH:

which compound has a molecular weight of 152.

Moreover, as previously noted, the subject composition, in addition tothe foregoing ingredients, also contains a lower alkanol. Representativeof useful alkanols, are those containing from 1 to 4 carbon atoms suchas methanol, ethanol, propanol and butanol, along with the iso formsthereof. Preferably, however, one employs methanol in the subjectcompositions both for reasons of cost and in addition because of itssuperior combustion with regard to the remaining alkanols.

In connection with the subject composition, one may employ from about 10to about 50% polyalkylene glycol and, preferably, from about to about30% by weight thereof. The remaining three ingredients with theexception of the alkanol should be present in an amount of from about0.01% to about 1% by weight of the total composition. Preferably,howelyer, one employs firorn about 0.3 to 0.8% of each of saidingredients. The remainder of the composition is comprised mainly of thealkanol, small portions of which may be substituted for furtheradditives such as dye-stuffs, anti-foaming agents and other conventionallubricative and fuel additives.

The subject composition may be prepared by solubilizing thehydroxy-containing aromatic ester, naturally derived ketone, and3-p-menthanol in the lower alkanol and subsequently combining theresulting mixture with the polyalkylene glycol. The subject compositionsmay then, as noted above, be utilized either as replacements for and/ oras additives to either fuels and/ or lubricants. In general, if one isformulating a fuel, the proportions set forth above are employed using ahigh viscosity polyalkylene glycol. As distinguished therefrom, if oneis formulating a crankcase lubricant, one would employ a low viscositypolyalkylene glycol in amounts of from about 75 to about 98% of thetotal composition. Moreover, one would employ from about 1 to about 10%of the remaining three additives and approximately 30% of the loweralkanol.

Subsequent to formulation the subject compositions may be added directlyto a lubricant oil and/or added 'to an engine as a replacement thereforor, as an alternative, may be injected into the carburetor throat usinga suitable 10 turbo-injector so as to form a vapor thereof which iscombustible.

The instant invention will now be illustrated by the following moredetailed examples thereof. It is to be noted, however, that the instantinvention is not deemed as being limited thereto.

EXAMPLE 1 A replacement for crankcase petroleum oil was preparedcomprising 96% of a mixture of mono-ether polyalkylene glycols having amolecular weight of approximately 1,000 and an ethyleneoxide-1,2-propylene oxide ratio of approximately 30/ 70, 5 cc. of3-p-menthanol, 5 cc. of Z-camphanone, 5 cc. of methyl salicylate, 30 cc.of methanol (99.2% anhydrous) and 5 cc. of dyestulf. The composition wasprepared by solubilizing each of the ingredients with the exception ofthe mono-ether polyalkylene glycol in the menthol and subsequentlycombining those so-solubilized products. The mixture may be used as asubstitute and/ or additive to crankcase oils so as to decreasepollution which results from the use of hydrocarbon residual oils.

EXAMPLE 2 A fuel was prepared comprising 25% of a mono-etherpolyalkylene glycol, having a molecular weight of approximately 900 andan ethylene oxide-propylene oxide ratio of approximately 50/50, 2 /z%methyl salycilate, 2 /2 3-p-menthanol, 2 /2 Z-camphanone, dyestutf, withthe remainder being methanol (99.2% anhydrous). The fuel mixture wasprepared by solubilizing each of the ingredients with the exception ofthe mono-ether polyalkylene glycol in the methanol and subsequentlycombining the so-formed mixture with the polyalkylene glycol. Themixture which resulted was suitable for injection as a vapor into thecarburetor of an internal combustion engine. Moreover, the resultingcomposition would result in a decreased pollution emission as a resultof the use thereof as compared to gasoline.

EXAMPLE 3 The preparation of Example 1 was once again prepared utilizingtherein of a mono-ether polyalkylene glycol having a molecular weight ofapproximately 1200 and an ethylene oxide-1,2-propylene oxide ratio ofapproximately 40/60 in lieu of the polyalkylene glycol employed therein.As a result of the above, a mixture which was found to be well suitedfor use as an additive to crankcase oils resulted.

EXAMPLE 4 The procedure of Example 2 was repeated utilizing therein 1%2-camphanone, 1% 3-p-menthan0l, and 1% methyl salycilate. The mixturewas formulated as in Example 3 and found to be a suitable fuelsubstitute.

Although the present invention has been adequately described in theforegoing specification and examples included therein, it is readilyapparent that various changes and modifications can be made, withoutdeparting from the spirit and scope thereof.

What is claimed is:

1. A composition for reducing pollutants emanating from the exhaust ofan internal combustion engine for use as a motor oil or motor fueladditive or motor oil substitute, which consists essentially of, incombination, a mixture of:

(1) a mono-ether polyalkylene glycol having an ethylene oxide topropylene oxide ratio of from about 75 1 l in an amount of from about 10to about 50% by weight of the total composition and exhibiting amolecular weight ranging from 500 to 5,000, and the remaining componentsof said composition with the exception of the alkanol being present inan amount ranging from about 0.01% to about 1.0% by weight of the totalcomposition. 2. The composition of claim 1, wherein said hydroxylcontaining aromatic ester is methyl salicylate.

3. The composition of claim 1, wherein said lower C -C alkanol ismethanol.

4. The composition of claim 1, wherein said aromatic ketone is a ketonehaving the formula:

5. In the process of operating an internal combustion engine utilizing ahydrocarbon lubricant therefor, the improvement which comprisessubstituting for at least a portion of said hydrocarbon lubricant, thecomposition of claim 1.

6. The process of claim 1, wherein said composition is substituted forall said hydrocarbon lubricant.

References Cited UNITED STATES PATENTS OTHER REFERENCES Kirk-OthmerEncycl. of Chem. TechnoL," vol. 10, 2nd Ed. (1966), PP- 658 and 659.

Chemical Abstracts 6th Collective Index, vols. 51-55 (1957-61), pp.71155, 71168 & 7119S.

Kirk-Othmer Encycl. of Chemical TechnoL, vol. 2 (1948), pp. 808 and 809;vol. 10 ('52), p. 19 and vol. 12 (54) p. 55.

DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner US.Cl. X.R.

